Abstract
Water is the renewable, bulk chemical that nature uses to enable carbohydrate production from carbon dioxide. The dream goal of energy research is to transpose this incredibly efficient process and make an artificial device whereby the catalytic splitting of water is finalized to give a continuous production of oxygen and hydrogen. Success in this task would guarantee the generation of hydrogen as a carbon-free fuel to satisfy our energy demands at no environmental cost. Here we show that very efficient and stable nanostructured, oxygen-evolving anodes are obtained by the assembly of an oxygen-evolving polyoxometalate cluster (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes. Our bioinspired electrode addresses the one major challenge of artificial photosynthesis, namely efficient water oxidation, which brings us closer to being able to power the planet with carbon-free fuels.
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References
Balzani, V., Credi, A. & Venturi, M. Photochemical conversion of solar energy. ChemSusChem 1, 26–58 (2008).
Gray, H. B. Powering the planet with solar fuel. Nature Chem. 1, 7 (2009).
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).
Meyer, T. J. Catalysis: the art of splitting water. Nature 451, 778–779 (2008).
Loll, B., Kern, J., Saenger, W., Zouni, A. & Biesiadka, J. Towards complete cofactor arrangement in the 3.0 Å resolution structure of photosystem II. Nature 438, 1040–1044 (2005).
Ferreira, K. N., Iverson, T. M., Maghlaoui, K., Barber, J. & Iwata, S. Architecture of the photosynthetic oxygen-evolving center. Science 303, 1831–1838 (2004).
Yano, J. et al. Where water is oxidized to dioxygen: structure of the photosynthetic Mn4Ca cluster. Science 314, 821–825 (2006).
Que, L. Jr & Tolman, W. B. Biologically inspired oxidation catalysis. Nature 455, 333–340 (2008).
Rappaport, F., Guergova-Kuras, M., Nixon, P. J., Diner, B. A. & Lavergne, J. Kinetics and pathways of charge recombination in photosystem II. Biochemistry 41, 8518–8527 (2002).
Ananyev, G. & Dismukes, G. C. How fast can photosystem II split water? Kinetic performance at high and low frequencies. Photosynth. Res. 84, 355–365 (2005).
Sartorel, A. et al. Polyoxometalate embedding of a catalytically active tetra-ruthenium(IV)-oxo-core by template-directed metalation of [γ-SiW10O36]8–. J. Am. Chem. Soc. 130, 5006–5007 (2008).
Geletii, Y. V. et al. An all-inorganic, stable, and highly active tetraruthenium homogeneous catalyst for water oxidation. Angew. Chem. Int. Ed. 47, 3896–3899 (2008).
Sartorel, A. et al. Water oxidation at a tetraruthenate core stabilized by polyoxometalate ligands: experimental and computational evidence to trace the competent intermediates. J. Am. Chem. Soc. 131, 16051–16053 (2009).
Liu, F. et al. Mechanisms of water oxidation from the blue dimer to photosystem II. Inorg. Chem. 47, 1727–1752 (2008).
Kanan, M. K. & Nocera, D. G. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 321, 1072–1075 (2008).
Mola, J. et al. Ru-Hbpp-based water-oxidation catalysts anchored on conducting solid supports. Angew. Chem. Int. Ed. 47, 5830–5832 (2008).
Brimblecombe, R., Swiegers, G. F., Dismukes, G. C. & Spiccia, L. Sustained water oxidation photocatalysis by a bioinspired manganese cluster. Angew. Chem. Int. Ed. 47, 7335–7338 (2008).
Cracknell, J. A., Vincent, K. A. & Armstrong, F. A. Enzymes as working or inspirational electrocatalysts for fuel cells and electrolysis. Chem. Rev. 108, 2439–2461 (2008).
Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).
Herrero, M. A. et al. Synthesis and characterization of a carbon nanotube–dendron series for efficient siRNA delivery J. Am. Chem. Soc. 131, 9843–9848 (2009).
Mašek, K. et al. SRPES investigation of tungsten oxide in different oxidation states. Surf. Sci. 600, 1624–1627 (2006).
Moulder, J. F., Stickle, W. F., Sobol, P. E. & Bomben, K. D. Handbook of X-Ray Photoelectron Spectroscopy (Perkin-Elmer, 1992).
Mackiewicz, N. et al. Supramolecular self-assembly of amphiphiles on carbon nanotubes: a versatile strategy for the construction of CNT/metal nanohybrids, application to electrocatalysis. J. Am. Chem. Soc. 130, 8110–8111 (2008).
Bi, L.-H. et al. Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis. Inorg. Chem. 48, 10068–10077 (2009).
Wightman, R. M. Probing cellular chemistry in biological systems with microelectrodes. Science 311, 1570–1574 (2006).
Lutterman, D. A., Surendranath, Y. & Nocera, D. G. A self-healing oxygen-evolving catalyst. J. Am. Chem. Soc. 131, 3838–3839 (2009).
Brimblecombe, R. et al. Sustained water oxidation by [Mn4O4]7+ core complexes inspired by oxygenic photosynthesis. Inorg. Chem. 48, 7269–7279 (2009).
Tinker, L. L., McDaniel, N. D. & Bernhard, S. Progress towards solar-powered homogeneous water photolysis. J. Mater. Chem. 19, 3328–3337 (2009).
Lacerda, L. et al. Dynamic imaging of functionalized multi-walled carbon nanotube systemic circulation and urinary excretion. Adv. Mat. 20, 225–230 (2008).
Carano, M., Holt, K. B. & Bard, A. J. Scanning electrochemical microscopy 49. Gas-phase scanning electrochemical microscopy measurements with a Clark oxygen ultramicroelectrode. Anal. Chem. 75, 5071–5079 (2003).
Acknowledgements
We thank M. Meneghetti for assistance with the RAMAN spectroscopy and discussion of the data. Financial support from Consiglio Nazionale delle Ricerche (CNR), Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR, PRIN Contract No. 20085M27SS), University of Padova (Progetto Strategico 2008, HELIOS, prot. STPD08RCX) the European Science Foundation's Cooperation in Science and Technology D40 action, Fondazione Cassa di Risparmio in Bologna and the University of Bologna is acknowledged.
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F.M.T. performed the synthetic tasks, optimized the deposition protocol and coordinated the characterization and electrocatalytic experiments; A.S. and M.C. contributed to the design, synthesis and characterization of the POM interface; C.M. carried out the SEM and AFM, and analysed the data; B.R.G. performed the HRTEM and STEM analyses; H.A. carried out the SAXS and analysed the data; L.C., A.G. and P.P. performed the XPS and analysed the data; F.P., M.M., S.R. and M.I. performed and analysed the electrochemistry experiments; T.D.R. discussed and supervised the functionalization of carbon nanostructure; G. Scorrano helped with the design and discussion of the experiments; G. Scoles helped with the design and discussion of the experiments, and contributed to writing the manuscript; M.P. and M.B. planned and supervised the research, analysed the data and co-wrote the manuscript.
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Toma, F., Sartorel, A., Iurlo, M. et al. Efficient water oxidation at carbon nanotube–polyoxometalate electrocatalytic interfaces. Nature Chem 2, 826–831 (2010). https://doi.org/10.1038/nchem.761
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DOI: https://doi.org/10.1038/nchem.761
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